Formation and Stability of Equiatomic and Nonequiatomic Nanocrystalline CuNiCoZnAlTi High-Entropy Alloys by Mechanical Alloying

Nanocrystalline equiatomic high-entropy alloys (HEAs) have been synthesized by mechanical alloying in the Cu-Ni-Co-Zn-Al-Ti system from the binary CuNi alloy to the hexanary CuNiCoZnAlTi alloy. An attempt also has been made to find the influence of nonequiatomic compositions on the HEA formation by varying the Cu content up to 50 at. pct (Cu _x NiCoZnAlTi; x = 0, 8.33, 33.33, 49.98 at. pct). The phase formation and stability of mechanically alloyed powder at an elevated temperature (1073 K [800 °C] for 1 hour) were studied. The nanocrystalline equiatomic Cu-Ni-Co-Zn-Al-Ti alloys have a face-centered cubic (fcc) structure up to quinary compositions and have a body-centered cubic (bcc) structure in a hexanary alloy. In nonequiatomic alloys, bcc is the dominating phase in the alloys containing 0 and 8.33 at. pct of Cu, and the fcc phase was observed in alloys with 33.33 and 49.98 at. pct of Cu. The Vicker’s bulk hardness and compressive strength of the equiatomic nanocrystalline hexanary CuNiCoZnAlTi HEA after hot isostatic pressing is 8.79 GPa, and the compressive strength is 2.76 GPa. The hardness of these HEAs is higher than most commercial hard facing alloys (e.g., Stellite, which is 4.94 GPa).     

Microstructures and properties of CoCrCuFeNiMox high-entropy alloys fabricated by mechanical alloying and spark plasma sintering

CoCrCuFeNiMox (x values in molar ratio, x?=?0, 0.2, 0.4 and 0.8) high-entropy alloys were prepared by mechanical alloying and spark plasma sintering method. The effects of Mo addition on microstructure and mechanical properties were investigated. The X-ray diffraction (XRD) result showed that the addition of Mo into CoCrCuFeNi high-entropy alloy (HEA) changed the original phase constitution from FCC to FCC?+?σ?+?μ and the peak intensity of (1 1 1) shifted to the left and decreased steadily. The field emission scanning electron microscope confirmed that the Cu-rich second FCC phase disappeared and the σ phase with a tetragonal structure expanded as the Mo content was increased. Additionally, a high density of dimple-like features were seen in CoCrCuFeNi HEA while typical quasi-cleavage facets could be observed from the fracture surfaces of the HEAs with the addition of Mo. The Mo0.8 alloy showed a good wear resistant and appropriate strength with fracture strain 22.70%, fraction coefficient 0.65, hardness 530?HV and compressive strength 1448?MPa.

Special theme block on high entropy alloys, guest edited by Paula Alvaredo Olmos, Universidad Carlos III de Madrid, Spain, and Sheng Guo, Chalmers University, Gothenburg, Sweden.     

Influence of zirconium addition on the microstructure,thermodynamic stability,thermal stability and mechanical properties of mechanical alloyed spark plasma sintered (MA-SPS) FeCoCrNi high entropy alloy

ABSTRACT

Equiatomic FeCoCrNi (Zr₀) and non-equiatomic FeCoCrNiZr_0.4 (Zr_0.4) high-entropy alloys (HEAs) were synthesised by mechanical alloying and spark plasma sintering. XRD analysis verified the formation of FCC and BCC solid solution phases in both alloys after 30?h of ball milling. While the SPS FeCoCrNi alloy contains both FCC and BCC solid solution phases, the FeCoCrNiZr_0.4 presents an FCC solid solution. The thermodynamic analysis showed that FeCoCrNiZr_0.4 is more stable with respect to the FeCoCrNi alloy. The phase stability of FeCoCrNiZr_0.4 was revealed up to ～800°C. The shear strength and hardness of the FeCoCrNi HEA improved with Zr addition. Failure analysis of the shear punch tested samples revealed a ductile fracture with dimple structure for FeCoCrNi and a brittle fracture with a smooth featureless surface for FeCoCrNiZr_0.4.     

Thermo-mechanical effects caused by martensite formation in powder metallurgy FeMnSiCrNi shape memory alloys

The paper reports solution treatment (ST) and mechanical alloying (MA) effects on the structure and static/dynamic mechanical behaviour of PM-MA’ed FeMnSiCrNi shape memory alloys associated with the formation of thermally and stress-induced martensite. The specimens were subjected to tensile pre-straining, in order to stress induce martensite and their gauges were cut and prepared for X-ray diffraction (XRD) as well as for optical and scanning electron microscopy (SEM). XRD patterns allowed determining the presence of large amounts of α′-body centred cubic (bcc) besides ε-hexagonal close packed (hcp) martensite and γ-face centred cubic (fcc) austenite. The decrease in the amount of α′-bcc at specimens ST’ed at 1273 and 1373?K, with increasing pre-straining degree, was confirmed by XRD patterns and SEM micrographs. Dynamic mechanical analysis (DMA) was performed by strain sweeps (SS). The SS-DMA graphs displayed storage modulus plateaux which were associated with the formation of ε-hcp martensite.     

Phase Evolution and Mechanical Properties of Nano-TiO2 Dispersed Zr-Based Alloys by Mechanical Alloying and Conventional Sintering

The present study deals with the synthesis of 1.0 to 2.0 wt pct nano-TiO₂ dispersed Zr-based alloy with nominal compositions 45.0Zr-30.0Fe-20.0Ni-5.0Mo (alloy A), 44.0Zr-30.0 Fe-20.0Ni-5.0Mo-1.0TiO₂ (alloy B), 44.0Zr-30.0Fe-20.0Ni-4.5Mo-1.5TiO₂ (alloy C), and 44.0Zr-30.0Fe-20.0Ni-4.0Mo-2.0TiO₂ (alloy D) by mechanical alloying and consolidation of the milled powders using 1 GPa uniaxial pressure for 5 minutes and conventional sintering at 1673 K (1400 °C). The microstructural and phase evolution during each stage of milling and the consolidated products were studied by X-ray diffraction (XRD), scanning electron microscopy and transmission electron microscopy (TEM), and energy-dispersive spectroscopy. The particle size of the milled powder was also analyzed at systemic intervals during milling, and it showed a rapid decrease in particle size in the initial hours of milling. XRD analysis showed a fine crystallite size of 10 to 20 nm after 20 hours of milling and was confirmed by TEM. The recrystallization behavior of the milled powder was studied by differential scanning calorimetry. The hardness of the sintered Zr-based alloys was recorded in the range of 5.1 to 7.0 GPa, which is much higher than that of similar alloys, developed via the melting casting route.     

Effect of alloying elements on martensitic transformation in the binary NiAl(β) phase alloys

The characteristics of the B2(β) to L1₀(β′) martensitic transformation in NiAl base alloys containing a small amount of third elements have been investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It is found that in addition to the normal Ll₀ (3R) martensite, the 7R martensite is also present in the ternary alloys containing Ti, Mo, Ag, Ta, or Zr. While the addition of third elements X (X: Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Ta, W, and Si) to the binary Ni₆₄Al₃₆ alloy stabilizes the parentβ phase, thereby lowering the M_s temperature, addition of third elements such as Co, Cu, or Ag destabilizes theβ phase, increasing the M_s temperature. The occurrence of the 7R martensite structure is attributed to solid solution hardening arising from the difference in atomic size between Ni and Al and the third elements added. The variation in M_s temperature with third element additions is primarily ascribed to the difference in lattice stabilities of the bcc and fcc phases of the alloying elements.     

Thermodynamic Basis of Non-equilibrium Phase Transformations of bcc β-Phase in Ti–Mo System

This study reports the experimental identification of transformation products of high temperature bcc β phase in Ti–xMo (x = 1, 7, 15, 25 wt%) alloys and aims to understand the transformations by thermodynamic modelling. The high temperature bcc β phase had undergone martensitic transformation in Ti–1Mo and Ti–7Mo alloys, resulting in acicular martensitic structure within large β grains. X-ray diffraction (XRD) analysis confirmed the martensite to be hcp (α′) and orthorhombic (α″) in Ti–1Mo and Ti–7Mo alloys respectively. Combined analysis of XRD and transmission electron microscopy (TEM) suggested the formation of fine plates of α″, omega (ω) and bcc β phases in Ti-15 and Ti-25 Mo alloys. Calculation of enthalpy of formation supported the stability of solid solution phase over the amorphous phase in the entire concentration range of Mo.     

Microstructure and properties of CrMnFeCoNi high-entropy alloy prepared by mechanical alloying and spark plasma sintering

The equiatomic ratio CrMnFeCoNi high entropy alloy (HEA) was prepared by mechanical alloying (MA) and spark plasma sintering. This paper reports the behaviour of MA, the phase formation, microstructure and mechanical properties of CrMnFeCoNi HEA. With the increase of milling time, solid solution with single FCC phase was gradually formed. The single FCC phase remained as matrix after SPS at 1373?K and 50?MPa. Ultrafine-grained microstructure and good mechanical properties were obtained: At room temperature, the as-sintered bulks exhibit an excellent combination of high compressive strength (2390?MPa) and high fracture strain (47%).     

Effect of Zr Addition on Microstructure and Properties of FeCrNiMnCoZr x and Al0.5FeCrNiMnCoZr x High Entropy Alloys

In this study, the effect of Zr addition on phase formation, microstructure, and hardness of FeCrNiMnCoZr _x and Al_0.5FeCrNiMnCoZr _x were investigated. High entropy alloys (HEA) were synthesized using arc melting technique in argon (Ar) atmosphere (x = 0, 0.1, 0.2, 0.3). Ingots were homogenized for 24 h at 900 °C in Ar atmosphere. Phase formation, microstructure and hardness of HEAs were investigated using field emission scanning electron microscope, X-ray diffraction and Vickers microhardness tester. Electron micrographs of HEAs showed majorly dendritic(DR) and interdendritic(ID) phases. For both FeCrNiMnCoZr _x and Al_0.5FeCrNiMnCoZr _x alloys, amount of ID phases is seen to increase with increased Zr content. Aluminium containing HEAs showed fine needle-shaped precipitates dispersed throughout the matrix phase. XRD results confirmed the presence of mixed FCC/BCC phases in FeCrNiMnCoZr _x alloys and BCC as majority phase in Al_0.5FeCrNiMnCoZr _x alloys. As the Zr content increased, hardness of HEA increased.     

Ternary alloying study of MoSi2

Ternary alloying of MoSi₂ with adding a series of transition elements was investigated by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive spectroscopy (EDS). Iron, Co, Ni, Cr, V, Ti, and Nb were chosen as alloying elements according to the AB₂ structure map or the atomic size factor. The studied MoSi₂ base alloys were prepared by the arc melting process from high-purity metals. The EDS analysis showed that Fe, Co, and Ni have no solid solubility in as-cast MoSi₂, while Cr, V, Ti, and Nb exhibit limited solid solubilities, which were determined to be 1.4±0.7, 1.4±0.4, 0.4±0.1, and 0.8±0.1. Micro-structural characterization indicated that Mo-Si-M_VIII (M_VIII=Fe, Co, Ni) and Mo-Si-Cr alloys have a two-phase as-cast microstructure, i.e., MoSi₂ matrix and the second-phase FeSi₂, CoSi, NiSi₂, and CrSi₂, respectively. In as-cast Mo-Si-V, Mo-Si-Ti, and Mo-Si-Nb alloys, besides MoSi₂ and C40 phases, the third phases were observed, which have been identified to be (Mo, V)₅Si₃, TiSi₂, and (Mo, Nb)₅Si₃.     

THE PREPARATION AND SOME PROPERTIES OF TUNGSTEN-RHENIUM-OSMIUM ALLOYS

Abstract

Two series of tungsten-rhenium-osmium alloys have been successfully prepared by powder-metallurgy techniques in sintered bar form. The first series, containing nominally 5% Re and up to 2·25% Os, are single-phase alloys consisting of an α solid solution of tungsten, rhenium, and osmium. The second series, containing nominally 26% Re and up to 11·3% Os, consist of the same solid solution up to ～1·67% Os, the higher osmium contents giving a two-phase alloy consisting of the α solid solution and the hard, brittle a phase. The two-phase alloys are of the age hardenable type and their properties are thus dependent on the thermal history.

The alloys containing ～26% Re and between ～0·69% and 4·5% Os are particularly prone to deformation twinning at room temperature, the tendency reaching a maximum at ～1·67% Os. This observation may be interpreted as an extension of the rhenium alloying effect, the double addition of rhenium and osmium giving an interactive as well as additive effect of Os atoms. Confirmation of the lower energy of the twinning planes is also apparent from the mode of precipitation of the σ phase on preferential planes in this composition range.     

Phase relationships and thermodynamic properties in the Mn-Ni-C system

In the present work, phase relationships in selected phase regions of the Mn-Ni-C system have been investigated at 1073 and 1223 K by use of an equilibration technique. Alloys of Mn-Ni-C were prepared from pure Mn, Ni, and C powders by the powder metallurgy method. The phase identification of the heat-treated samples was carried out by scanning electron microscope (SEM) and transmission electron microscope (TEM). The main phase compositions of the alloys have been analyzed by X-ray diffraction (XRD). The experimental results show that the site fraction of Ni in the metallic sublattice of the carbides M₂₃C₆, M₇C₃, and M₅C₂ is quite low and the value is around 0.02 to 0.03. The thermodynamic activities of manganese in 16 different Mn-Ni-C alloys have been studied by solid-state galvanic cell technique with single-crystal CaF₂ as the solid electrolyte in the temperature range 940 to 1165 K. The results are discussed in light of the available thermochemical information.     

High Temperature Phase Stability and Microstructural Characterization of D9 Stainless Steel-Zirconium Metal Waste Form Alloys

Zirconium present in stainless steel-zirconium metal waste form (MWF) alloys form Ni?CZr and Fe?CZr intermetallic phases which act as a sink for radionuclide and improve resistance to localized corrosion as well as selective radionuclide leaching. The present study looks into the behavior of Zr intermetallics in MWF alloys with the variation of Zr content after heat treatments. Two MWF alloys of D9 SS (Ti modified 15Cr?C15Ni?C2.5Mo stainless steel) with 8.5 and 17?wt% Zr were heat treated at 1,323?K for 2 and 5?h and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The stability of the Zr intermetallic compounds was examined by high temperature XRD. The results from XRD study showed the presence of NiZr, Ni₅Zr, Ni₇Zr₂, FeZr₂, and Fe₃Zr peaks along with fcc Fe based solid solution. The MWF alloy with 17?wt% Zr exhibited ??-ferrite peak in as-cast condition which was not observed after heat treatment. From the SEM micrograph the agglomeration of intermetallic phases was observed after heat treatment and the grain size of the intermetallic phases increased with duration of heat treatment. The high temperature XRD study revealed that all the intermetallic phases were stable up to 1,173?K and above this temperature Ni?CZr intermetallics started disappearing. However Fe?CZr intermetallics were stable till 1,373?K. The paper presents the high temperature phase stability of D9 SS-Zr MWF alloys.     

Phase transitions in reactive formation of Ti5Si3/TiAl in situ composites

A new method is developed for preparing Ti₅Si₃/TiAl in situ composites by incorporating metastable phases (called metastable precursors) into TiAl (a mixture of elemental Ti and Al) matrix powders. Metastable precursors with a starting composition of Ti-14Al-21Si are prepared by mechanical alloying (MA). They have been proven through X-ray diffraction (XRD) analysis and transmission electron microscope (TEM) observations to be mainly consisting of mixtures of nanostructured solid solutions and milling-formed TiAl compound. Particularly, phase reactions and transitions in the precursors and the composites during heating have been investigated in detail by using diffraction thermal analysis (DTA) in conjunction with XRD. It has been found that Ti₅Si₃ is in situ formed through a phase transition chain, TiSi₂ → Ti₅Si₄ → Ti₅Si₃. When the composite powder (precursor, Ti and Al) is heated, a combustion reaction first occurs in the matrix, which results in the formation of TiAl₃ and/or TiAl followed by the completion of the previously mentioned silicide transitions in a very short time. Scanning electron microscope (SEM) observations indicated the locations of reinforcements in the reaction-formed composite, and TEM observation provided some details of the structures for the reinforcements and their neighborhood. This method is intriguing because a designed phase hierarchy is possible.     

内燃机用粉末烧结Ti-21.5Nb合金组织与力学性能研究

采用放电等离子烧结技术制备内燃机用Ti-21.5Nb-2Zr-1.2Mo-0.1Y钛合金材料(Ti-21.5Nb), 并对其进行固溶和时效处理, 通过扫描电子显微镜、金相显微镜、X射线衍射仪、万能拉伸测试仪等设备分析试样的微观形貌、组织结构、物相组成以及力学性能。结果表明: 采用等离子旋转电极法制备的预合金球形粉末相对密度较高, 并且未形成孔洞; 烧结试样和固溶试样都是由β相与α相组成, 放电等离子烧结Ti-21.5Nb合金和常规铸锭合金具有相同的相结构变化规律; 合金烧结组织由β等轴晶和一些小尺寸α相构成, 其中β等轴晶的粒径介于30~80μm; 在800 ℃下对烧结试样进行固溶时效处理, 得到的固溶组织主要是由β相构成, 同时在β相中还生成了椭球形α弥散组织; 在500 ℃下对Ti-21.5Nb固溶试样进行时效处理, 在合金基体中析出ω相, 而原先的α相全部消失; 在380 ℃时效处理时, 组织中只存在α相, ω相完全消失; 在800 ℃对Ti-21.5Nb合金进行固溶时效处理可以获得力学性能更优的钛合金材料。     

Phase relationship of Dy-Fe-Mn system at 773 K

Rare-earth intermetallic compounds formed in many R-Fe-Mn（R=rare-earth element） systems exhibit excellent properties. In order to understand the existence and stability of the compounds in the system and further search for the potential application of R-Fe-Mn alloys in various aspects, it is necessary to investigate the phase relations of the Dy-Fe-Mn ternary system. A total of 96 samples of the Dy-Fe-Mn alloys were prepared by arc-melting and examined by metallographic analysis, X-ray diffraction（XRD）, scanning electron microscopy（SEM） and energy dispersive spectroscopy（EDS） techniques. The phase relationship of the Dy-Fe-Mn system at 773 K was determined. It was found that the isothermal section was characterized by intermediate solid solutions based on the substitutions of Fe/Mn atoms and the large extensions of the binaries into the ternary domains. The solid solubilities of the third element in the binary compounds and the phase boundaries were also determined by XRD technique using the phase disappearing method combined with the lattice parameter method and SEM/EDS technique. Two pairs of corresponding binary compounds in the Dy-Fe and Dy-Mn systems（DyFe2 and DyMn2, Dy6Fe23 and Dy6Mn23） formed a continuous series of solid solution at 773 K, respectively.     

Microstructural characterisation of Ti–Nb–(Fe–Cr) alloys obtained by powder metallurgy

Abstract

β alloys based on the Ti–Nb alloy system are of growing interest to the biomaterial community. The addition of small amounts of Fe and Cr further increases β-phase stability, improving the properties of Ti–Nb alloy. However, PM materials sintered from elemental powders are inhomogeneous due to restricted solid state diffusion and mechanical alloying provides a route to enhance mixing and elemental diffusion. The microstructural characteristics and bend strength of Ti–Nb–(Fe–Cr) alloys obtained from elemental powder mixture and mechanical alloyed powders are compared. Mechanical alloying gives more homogeneous compositions and particle morphology, characterised by rounded, significantly enlarged particles. In the sintered samples α and β phase are observed. The α phase appears at the grain boundaries and in lamellae growing inward from the edge, and is depleted in Nb. The β phase is enriched with Nb, Fe and Cr. The addition of Fe and Cr significantly increases the mechanical properties of Ti–Nb alloys, providing increased ductility.     

Morphology Transition from Dendrites to Equiaxed Grains for AlCoCrFeNi High-Entropy Alloys by Copper Mold Casting and Bridgman Solidification

The AlCoCrFeNi high-entropy alloys (HEAs) were prepared by the copper mold casting and Bridgman solidification. X-ray diffraction (XRD) results verify that the main phase was body-centered-cubic (bcc) solid solution by these two solidification processes, indicating its good phase stability. Interestingly, the metallographic photos show a morphology transition from dendrites to equiaxed grains after Bridgman solidification, which was considered to have a strong dependence on the parameter of the G/V (the temperature gradient to the growth rate ratio). Compared to the as-cast sample, the plasticity of alloys synthesized by Bridgman solidification was improved by a maximum of 35?pct.     

Rapid solidification processing of a Mg-Li-Si-Ag alloy

A Mg-13Li-4Si-lAg (wt pct) alloy with improved ductility and thermal stability was developedvia the rapid solidification (RS) processing technique. Silicon was added to the alloy as the third alloying element in order to form a thermally stable intermetallic dispersoid phase required for improved mechanical properties at ambient and elevated temperatures. The microstructure of the as-spun and heat-treated alloy was characterized using differential scanning calorimetry (DSC), X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Microhardness measurements were conducted on as-spun and heat-treated alloy in order to obtain qualitative prop-erty data and to investigate the extent of the degradation of properties at elevated temperatures. It was found that the melt-spun Mg-Li alloy possessed a microstructure consisting of a fine dispersion of Mg₂Si phase in a fine-grained body-centered cubic (bcc) Mg-Li solid solution, resulting in the desired improvements in thermal stability and mechanical properties. Formerly Graduate Student, Department of Materials Science and Engineering, University of California     

Low temperature microwave sintering of Cu0.7Ni0.3(Al2O3) nanocomposite

In the present study, the effects of microwave sintering (MWS) on microstructural, tribological and corrosion properties of Cu_0.7Ni_0.3-5?wt-% Al₂O₃ nanocomposites were evaluated. The Cu and Ni powders along with Al₂O₃ nanopowder were mixed in a high-energy ball mill. The XRD patterns indicating formation of Cu_0.7Ni_0.3 solid solution alloy during mechanical alloying process. The mechanically alloyed powders were compacted by coldpress, and sintered samples at 200 and 300°C for 30 and 60?min by means of conventional sintering and MWS. Tribological properties of sintered samples were evaluated by ball-on-disk wear test. For MWS, results indicate that increasing the MWS temperature decreased the wear rate about 30%. Corrosion behaviour of nanocomposites were studied by cyclic potentiodynamic polarisation in 1?M NaOH solution and was found that corrosion current density of microwave sintered sample was decreased almost 35 times of that for conventional sintered sample.